Method for dyeing hair and anthraquinone dyestuff composition

ABSTRACT

NEW HAIR DYEING COMPOUND RESPONDING TO THE FORMULA   1-(CH3-CO-NH-(CH2)N-NH-)ANTHRAQUINONE   IN WHICH N IS A WHOLE NUMBER LYING BETWEEN 2 AND 6 INCLUSIVE AND METHOD FOR MAKING THE SAME AS WELL AS AN AQUEOUS SOLUTION THEREOF AS A COMPOSITION FOR DYEING HAIR.

United States Patent 54,036 Int. Cl. D06p 1/42; C09b 1/50 U.S. Cl. 8-103 Claims ABSTRACT OF THE DISCLOSURE New hair dyeing compound respondingto the formula 3) ITIH-(CHz) n-NHC 0 CH2 in which n is a whole numberlying between 2 and 6 inclusive and method for making the same as Wellas an aqueous solution thereof as a composition for dyeing hair.

The present invention relates to a new chemical compound responding tothe following general formula:

in which n is a whole number lying between 2 and 6 inelusive.

In accordance with the invention the compound of Formula I is obtainedby brominating l-N-acetylaminoalkylamino anthraquinone responding to theformula:

in which n has the significance hereinbefore indicated. reacting theresulting product with fuming sulfuric acid in the presence of boricacid so as to replace the bromine atom previously attached at position 4with a hydroxy radical, and then hydrolyzing the product in an acidmedi- It should be noted that the dyes of Formula I yield especiallyvaluable results when used to dye keratinic fibers, and particularlyhuman hair. These dyes are, to a substantial extent, soluble in water,and have a remarkable aflinity for keratinic fiber.

Their use in dyeing compositions makes it possible to obtain veryintense violet shades with a greater resistance to washing than can beobtained with those anthraquinone dyes having an analagous chemicalstructure heretofore known, which have a tertiary amine function at theend of the chain attached to position 1 in Formula I.

The present invention relates to a composition for dyeing keratinicfibers, and in particular human hair, which is essentially characterizedby the fact that it comprises, in aqueous solution, at least one dyeresponding to Formula I. In a preferred embodiment of the invention thepH of the dyeing compositions according to the invention lies between 6and 12, and is preferably about 9.

The concentration of the dyes of Formula I in the dyeing compositionsaccording to the invention may vary within broad limits, but ispreferably between 0.01% and 3%.

The dyeing compositions according to the invention may be used attemperatures between 5 and C., but are preferably applied at roomtemperature.

The dyeing compositions according to the invention may also containwetting agents, dispersing agents, penetrating agents, perfumes andlacquers, and any other ingredients conventionally included in hairdyeing compositions. They may also contain other dyes than thoseresponding to Formula I, and particularly anthraquinone, azo, and nitrodyes.

The present invention also relates to a method of dyeing keratinicfibers and particularly human hair, essentially characterized by thefact that the hair is impregnated with an aqueous solution containing atleast one dye responding to the Formula I for from 5 to 30 minutes,after which it is shampooed, rinsed and dried.

In order that the invention may be better understood, a method ofpreparing a dye responding to Formula I, and several examplesillustrating the use of said dye on hair, will now be described, purelyby way of illustration.

EXAMPLE 1 Preparation of 1- -aminopropylamino-4-hydroxy anthraquinonemonohydrochloride The preparation may be schematically represented inthe following form:

First step: Preparation of 1-'y-acetylaminoproylamino- 4-bromoanthraquinone 0.03 mole (9.66 g.) of l-y-acetylaminopropylaminoanthraquinone is dissolved in 100 cc. of acetic acid at um so as tode-acetylate the chain attached at position 1. 50 C. 0.03 mole (2.4 g.)of sodium acetate is added, followed by 0.03 mole (4.8 g.) of bromine,which is added little by little, while stirring. The reaction mixture iskept at 50 C. for 7 hours, and then at 20 C. for 15 hours, and thenpoured into water. The crude product is dried and washed in hot alcohol.The result is 6.3 g. of 1-'yacetylaminopropylamino-4-bromo anthraquinonewhich, after recrystallization in methylisobutylketone, melts at 187 C.

Analysis of this product yields the following results:

Analysis.Calculated for C19H17N203Br (percent): C, 56.86; H, 4.24; N,6.98; Br, 19.95. Found (percent): C, 56.79-56.89; H, 4.43-4.43; N,7.10-6.96; Br, 19.54-19.32.

Second step: Preparation of l-q acetylaminopropylamino-4-hydroxyanthraquinone 0.0238 mole (9.5 g.) of 1-'y-acetylaminopropylamino-4-bromo anthraquinone is heated for 4 hours at 120 C. in the presence of95 g. of fuming sulfuric acid and 4.75 g. of boric acid. After cooling,the reaction mixture is poured over cracked ice and neutralized with asodium hydroxide solution. 10 cc. of of acetic anhydride is added andthe mixture heated for 30 minutes at 70 C. After cooling, drying andwashing with water yields 7.7 g. of 1 'yacetylaminopropylamino-4-hydroxy anthraquinone which, afterrecrystallization in chlorobenzene, melts at 198 C.

Analysis of this product yields the following results:

Analysis.--Calculated for C H N O (percent): C, 67.46; H, 5.32; N, 8.28.Found (percent): C, 67.59-67.53; H, 5.49-5.41; N, 8.15-8.10.

Third step: Preparation of 1-'y-aminopropylamino- 4-hydroxyanthraquinone monohydrochloride 0.0133 mole (4.5 g.) of1-'y-acetylaminopropylamino-4- hydroxy anthraquinone is added to 10 cc.of 50% hydrochloric acid. The mixture is then heated at reflux for twohours and vacuum dried. The residue is redissolved in acetone and dryingyields 4.4 g. of 1-y-aminopropylamino- 4-hydroxy anthraquinonemonohydrochloride, which, after recrystallization in a mixture of waterand isopropanol, melts and decomposes at 269 C.

EXAMPLE 2 The following dyeing composition is prepared:

1-'y-aminopropylamino-4-hydroxy anthraquinone monohydrochloride0.33 g.

Lauric alcohol with 10.5 moles of ethylene oxide-2 g.

2 N solution of Na CO q.s.p.-pH=7 Water, q.s.p.-100 g.

This composition is applied to bright golden chestnut hair, and left toact for 10 minutes, after which the hair is shampooed and rinsed. Avioline chestnut is obtained.

EXAMPLE 3 The following dyeing composition is'prepared:

1-'y-aminopropylamino-4-hydroxy anthraquinone monohydrochloride0.17 g.

4 1 N,N dimethylamino 3-5 aminoethylamino-4-nitro benzene-0.11 g. Lauricalcohol with 10.5 moles of ethylene oxide-3 g. Monoethanolamine,q.s.p.-pH=9' Water, q.s.p.- g.

ll 1 0 OH wherein n is an integer of 2-6 inclusive, said dye beingpresent in amounts of about 0.01-3 weight percent of said composition,permitting said composition to remain in contact with said hair for aperiod of about 5-30 minutes,

washing, rinsing and drying said hair.

2. A composition for dyeing human hair comprising an aqueous solution ofan anthraquinone dye having the formula wherein n is an integer of 2-6inclusive, said dye being present in amounts of about 0.01 weightpercent of said composition.

3. The composition of claim 2 having a pH between 6-12.

References Cited UNITED STATES PATENTS 2,659,739 11/1953 Dickey 2603803,153,059 10/1964 Straley et al. 260-380X 3,442,995 5/ 1969 Kalopissiset al. 8-10X GEORGE F. L'ESMES, Primary Examiner P. C. IVES, AssistantExaminer US. Cl. X.R.

